Triacylglycerol oligomer products and methods of making same

ABSTRACT

The present invention relates generally to triacylglycerol oligomer products and triacylglycerol-derived products and methods of making, using and producing same.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to triacylglycerol oligomer products and triacylglycerol-derived products and methods of making, using and producing same.

2. Description of the Related Art

Triacylglycerols (TAGS) are lipids of plant or animal origin. They include such common substances as safflower oil, canola oil, peanut oil, corn oil, cottonseed oil, sunflowerseed oil, linseed oil, soybean oil, tung oil, etc. Those TAGS that are liquids at room temperature are generally known as oils; those that are solids are usually known as fats. TAGS are simply the fatty acid esters of the triol glycerol.

The general structure of TAGS is:

The fatty acids, R₁, R₂, R₃, that are obtained by hydrolysis of naturally occurring fats and oils are long, straight-chain carboxylic acids with about 12 to 20 carbon atoms. Most fatty acids contain an even number of carbon atoms. Some of these common fatty acids are saturated, while others have one or more elements of unsaturation; generally carbon-carbon double bonds.

TAGS naturally occur in some plants and can be obtained in relative pure forms by various processing methods. Substances such as free fatty acids and phospholipids are removed during processing. TAGS resulting from a single plant source, after processing, are typically a mixture made up of TAGS with differing percentages of saturated and unsaturated fatty acids. Table 1 lists the approximate composition of the fatty acids obtained from hydrolysis of some TAGS. Table 2 lists the supply of major TAGS produced in the United States. TABLE 1 Fatty Acid Composition Obtained by Hydrolyhsis of Common Triacylglycerols ELEO- TAG MYRISTIC PALMITIC STEARIC OLEIC LINOLEIC STEARIC LINOLENIC SOYBEAN 1-2 6-10 2-4 20-30 50-58 5-10 COTTON 1-2 18-25  1-2 17-38 45-55 SEED CORN 1-2 7-11 3-4 25-35 50-60 LINSEED 4-7  2-4 14-30 14-25 45-60  SUNFLOWER 6-7  1-2 21-22 66-67 TUNG 80

TABLE 2 Major TAGS produced in the United States. TRIACYLGLYCEROL PRODUCTION (POUNDS) SOYBEAN 20,220,000,000 COTTONSEED 1,210,000,000 SUNFLOWERSEED 1,196,772,000 CORN 1,283,200,000

TAGS containing multiple double bonds within their carboxylic acid moieties undergo thermal polymerization to form oligomers which are low molecular weight polymers. Triacylglycerol Oligomers (TAGOS) were first described by Schieber (1928).

Several investigators, Schieber (1928, 1929), Kappelmier (1933, 1938), Kurz (1936), Bradley (1940), Phalnikar and Bhide (1944), Bradley (1947), Barker, Crawford, and Hilditch (1951), Wisenblatt, Wells, and Common (1953), Wells and Common (1953), Pascual and Detera (1966), Boelhouwer, Knegiel, and Tels (1967), Saha and Bandyopadhyay (1974), Sarma (1984) have suggested mechanisms for thermal polymerization of vegetable oils. Scheiber (1928, 1929) and Kappelmeier (1933, 1938) proposed a Diels-Alder diene synthesis as a basis for explaining the polymerization of vegetable oils which is often referred to in the literature. Most investigators agree that the formation of hydroxy unsaturated dimeric acids occurs during thermal polymerization and are connected by means of a cyclic compound.

Paper products have a vital role in many of society's activities and basic needs. Since the price of paper is increasing continuously and sources for production of paper is decreasing gradually, the U.S. paper industry has had to resort to more and more alternate fiber sources, e.g., recycled wastepaper. In 1993 for the first time in U.S. history, as much wastepaper was recycled as was land-filled and in 1994 the recovery rate for wastepaper and paperboard was greater than 40% consumption (Hutten, 1996). The recovery goal is 100% of all wastepaper and paperboard. The primary barrier to increased use of recycled paper are contaminants, which include stickies and short fiber lengths (fines), and successive recycles which continually decrease the quality of the recycle pulp. When newsprint was recycled seven times (Hayashi, 1979), it showed a sharp decrease in breaking length after the first cycle. The decrease leveled off thereafter to 70% of the original value. The oil absorption (printability) and opacity of paper prepared from the recycle pulp was inferior to that of the original paper. The deterioration was attributed to hardening of the pulp. The strength loss could be somewhat recovered by treatment with NaOH during the recycling process. Also mixing recycled pulp with virgin pulp increased the quality of the recycled paper. Loss of mechanical properties in a recycled pulp can be recovered by blending recycled fibers with virgin pulp fibers (Nada, et al, 2001). Addition of additives, e.g., polyvinyl alcohol, new pulp, or paper shaving, at certain percentage levels, improved these properties (El-Meligy, et al, 2001). Recycling of wastepapers helps to get rid of pollution, which results from burning accumulation of these wastepapers, including an increased percentage of CO₂. Use of recycle pulp reduces the need for trees from which virgin pulp is obtained. An opportunity exists to replace virgin pulp and other additives that are used to improve the properties of recycle pulp with a substance that is economically feasible, renewable, biodegradable, and petroleum-free. Modification of recycle pulp with soybean oligomers lend itself as one solution to this problem.

Evidence for the formation of intrapolymeric glycerides during thermal polymerization of linseed oil and soybean oil (Wisenblatt, et al, 1953) was obtained. This evidence clearly established an increase in free fatty acid content during thermal polymerization. Further data gave evidence of intrapolymeric glycerides or dimeric acids formed during thermal polymerization. It is suggested that these intrapolymeric glycerides or dimeric acids combine with an alcoholic group of cellulose to form an ester linkage. Synthesis and characterization of long chain fatty acid cellulose ester (FACE) have been reported in the literature. FACE have been synthesized by the acid chloride-pyridine reaction with different degrees of substitution (Wang, et al, 1994). A variety of long chain fatty acid esters of polymeric and oligomeric glucan carbohydrates have been synthesized and characterized. Formation of biopolymers and polyesters from soybean oil and carbohydrates were formed using polymerized soybean oil (Tao, 2003). Soybean oil was first polymerized. The optimum condition for the polymerization was at 350° C., 0.0025% iodine for 20 min at argon atmosphere. The polymerized soybean oil was then distilled for isolating high molecular weight soybean oil polymers. By the mass spectrometry analysis, it was found that these high molecular weight polymers were monocyclic dimers formed by the Diels-Alder reaction. These dimers then reacted with maltotriose or cellulose to form dimer fatty acid carbohydrate esters. It has been found that the dimer fatty acids can form high degree of substitution with maltotriose but not cellulose. The dimer fatty acid maltotriose ester was hard and rigid and solid.

The terminal alkyne ester is formed from the hydrolysis of the ester by cleavage of the alkyl-oxygen bond (Cohen, et al, 1941). Omitting considerations of mechanism, the normal rupture of the acyl-oxygen bond leads to ester interchange, while the rupture of the alkyl-oxygen bond will form an acid and an ether. The formation of these products, an acid and an ether, by the alcoholysis of an ester, must, in the absence of another mechanism for their production, be considered valid evidence for the cleavage of the ester at the alkyl-oxygen bond. This mode of reaction, leading to these products is shown by esters of strong acids, both mineral and organic.

Various modifications of cellulose increased the physical and optical properties of paper. Paper with improved strength properties was prepared from carboxymethylated bleached kraft pulp (Fahmy, et al, 1972). Results from a study (Choi, et al, 2001) conducted to evaluate the different chemical additives (sizing and wet strength resins) on newsprint composed of different furnished are reported. To assess the impact of water intake and wet strength for various blends, a number of commercially produced newsprint sheets based on thermomechanical as well as deinked pulp (TMP and DIP) were tested. The effect of internally added chemical additive types (e.g., cationic rosin, cationic glyoxylated polyacrylamide, cationic polyamidomine-epichlorohydrin resins, cationic alkylketenedimer (AKD), and an AKD/alkenyl succinic anhydride mixture) at application levels on various paper properties relating to newsprint runnability and printability were examined. Contact angle, dynamic dimensional changes in a short time frame, water uptake, and strength loss were examined. Wet strength resins as well as sizing agents help both DIP and TMP newsprint to maintain strength when they contact water. The effect of wet strength resin is greater than the effect of sizing agents in maintaining wet strength in DIP newsprint while sizing is more effective at controlling cross-machine direction hygro-expansion. Sizing agents are predicted to be effective in reducing water-related expansion, misregistration, and break problems. Wet strength resins are predicted to be effective in improving machine direction wet strength and reducing breaks in situations where water is heavily applied. Cationic ethers were prepared from oat starch by reaction with 2-chloro-3-hydroxypropyltrimethylammonium chloride (1) at alkaline pH (Lim, et al, 1992). The reaction of starch (approximately 35% solids) in a mixture of 0.5M Ca(OH)₂ and 0.49M CaCl₂ at 25° C. for twenty hours with 50 mmol (1) per mmol of anhydroglucose unit gave cationic starch with DS of 0.014. When the reaction was done in 0.48 M NaOH and 2.43 M Na₂SO₄, the degree of substitution was 0.042. Cationic oat starch, cornstarch, and wheat starch, all with DS of approximately 0.013, improved the strength of paper hand sheets to a comparable degree. Cationic oat and wheat starches prepared in CaCl₂—Ca(OH)₂ gave higher Scott bond and burst indexes than those prepared in NaOH—Na₂SO₄. Gums have also been used as paper strengthening agents. A simple process was developed (Pamplona, et al, 1990) to produce a dry-strengthening gum additive for paper locally grown giant ipilipil seeds by grinding and cooking the ground seeds in water at 70° C. to 80° C. The gum was then tested as a dry-strengthening agent for pulp handsheets made from various types of pulps. The dry-strength of each pulp sample used was increased.

Modified TAGOS, such as soybean oligomer modified pulp (SBOMP), provide environmental benefits in that (1) they reduce the use of trees which are the main source for virgin pulp, (2) they contain no petroleum-based products, and (3) they are produced from renewal resources. The cost of TAGOS are less than the cost of virgin pulp which provides an economic benefit. By reducing the need for trees to produce virgin pulp, the destruction of our forests is reduced providing a social benefit. Technical benefits are attributed to the process having applications in other industries where cellulose is used such as the textile industry.

Therefore, there exists a need in the art for new and improved compositions for improving the properties of recycled paper and absorbent products, as well as methods of using same, that overcome the disadvantages and defects of the prior art. It is to such compositions and methods wherein modified TAGOS act as a strengthening agent that the present invention is directed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a perspective side view of the degummer assembly of the present invention.

FIG. 2 is a second perspective side view of the degummer assembly of the present invention.

FIG. 3 is a schematic flow diagram.

FIG. 4 is a flow diagram of the thermal polymerization process of TAGS.

FIG. 5 is an infrared spectra comparing the formation of alkyne-ether linkages between 730 cm⁻¹ and 580 cm^(−1.)

FIG. 6 is an infrared spectra comparing the formation of alkyne-ether linkages between 2135 cm⁻¹ and 2085 cm^(−1.)

FIG. 7 is an infrared spectra comparing cotton treated with soybean oligomer Z-6 and soybean oligomer Z-6 (cured).

FIG. 8 is an infrared spectra comparing untreated cotton and cotton treated with soybean oligomer Z-6.

DETAILED DESCRIPTION OF THE INVENTION

Before explaining in detail at least one embodiment of the invention in detail by way of exemplary drawings, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for purpose of description and should not be regarded as limiting.

1. Removal of Lecithin (Degumming)

Lecithin is a mixture of phospholipids, cephalin and inositol phosphatides, glycerides, traces of tocopherols and pigments. Phospholipids are lipids that contain groups derived from phosphoric acid. The most common phospholipids are the phosphoglycerides, which are closely related to common fats and oils. A phosphoglyceride generally has a phosphoric acid goup in place of one of the fatty acid groups of TAGS. The simplest class of lecithin are the phosphatidic acids, which consist of glycerol esterified by two fatty acids and one phosphoric acid group. Phosphatidic acid is represented by the chemical formula given below.

Lecithin can be hydrated with water which renders it immiscible with oil and brings about a separation of hydrated lecithin and oil. However, hydrated lecithin when mixed thoroughly with water and TAGS forms a very stable emulsion that separates only on standing for long periods of time. Formation of the emulsion can be avoided by bubbling TAGS through a container filled with water. A bubble chamber (degummer) was developed for this purpose.

The degummer assembly 10 of the present invention is show in FIGS. 1 and 2. The degummer assembly 10 consists of a tank member 20 having an inlet 30, at least one outlet 40, and an interior reaction chamber 50. The inlet 30 and the at least one outlet 40 are in open fluid communication with the interior reaction chamber 50. A plate 60 containing small holes 70 of known diameter is placed at the bottom 80 of the tank member 20 and attached to inlet 30. The interior reaction chamber 50 is filled with a liquid medium 90 such as water or other liquids (bulk liquid) and maintained at a temperature which can range from <25° C. to >60° C. Water hydrates the lecithin.

TAG is pumped or gravity fed into the interior reaction chamber 50 through the small holes 70 and form bubbles 100 or “strings” on contact with the liquid medium 90 and do not form emulsions. The small bubbles 100 or “strings” of TAGS rise to the surface of the bulk liquid and burst forming at least two separate liquid phases 110, (i.e., at least two reaction products) each of which remain separated from the liquid medium 90. At least one liquid phase contains degummed TAG 120, at least one liquid phase contains lecithin 130, and the third is the liquid medium 90.

As more and more TAG is fed into the tank member 20, the degummed TAG 120, which is less dense than the lecithin 130 rises to the top 140 of the interior reaction chamber 50 and forms a top layer 150. The lecithin 130 forms the middle layer. The lower layer is the liquid medium 90. The top layer 150 containing the degummed TAG 120 is allowed to reach a certain height to minimize contamination from the lecithin 130 at which time it can be continuously removed through the at least one outlet 40. The lecithin 130 can be removed through a lower at least one outlet tube 41. The volume produced depends on degummer assembly 10 variables such as the diameter of the small holes 70 of the inlet 30, size of the tank member 20, the flow rate, liquid medium 90 temperature, etc. Degummed TAG 120 was analyzed for phosphorous content. The results are given in Table 3 below. TABLE 3 Phosphorous Content of Degummed Triacylglycerols (TAGS) TRIACYLGLYCEROL PHOSPHOROUS, PPM* SOYBEAN 0.005

Van Nieuwenhuyzen (1976) demonstrated that the viscosity of lecithin at a temperature of 70° C. increases as the moisture content decreases. The viscosity of the lecithin continues to increase until it achieves a moisture content of approximately 7%. The viscosity of the lecithin then begins to decrease rapidly until it is dry. This property of lecithin was used to develop a process to reduce the moisture content to less than 3%.

TAGS that have been degummed according to the procedure given above are further refined by vacuum distillation of free fatty acids. The first step in the vacuum distillation process is to remove under vacuum a large portion of the oxygen before heat is applied. Once the oxygen is removed under vacuum, heat is gradually applied until the boiling point temperature of the free fatty acids has been reached at the operating vacuum. The temperature is maintained until all fatty acids have been removed. The resulting refined TAGS are then ready for thermal polymerization.

A continuous semi-plugged flow reactor has been designed for the refining of TAGS. All columns are under the same vacuum. Degummed TAG at room temperature is pumped into a first column and removal of oxygen begins. As TAG flows upward through the column and once the temperature increases to about 60° C., the TAG exits into column two. As it flows upward through column two, oxygen is still being removed as the temperature gradually increases to about 120° C. Columns three, four, and five are utilized for gradually increasing the TAG to the boiling point of free fatty acids at the operating vacuum and holding it for a period of time depending on the flow rate in order to allow complete removal of the free fatty acids. At a temperature of from about 228° C.-235° C., the TAG undergoes a color change from “straw” to a light greenish tint. The results are shown in Table 4. TABLE 4 Data for Refined Triacylglycerols FREE FATTY ACID - TRIACYLGLYCEROL Y* R* B* %* SOYBEAN 2.8 1.4 92.0 COTTONSEED SUNFLOWERSEED CORN

TAGOS are prepared by thermal polymerization of TAGS that have been degummed and refined according to the procedures given above. Pre-polymerization and polymerization takes place in columns six through ten shown in FIG. 4.

Column six is the pre-polymerization reactor column wherein the temperature is gradually increased from the boiling point of the free fatty acids to polymerization temperature. TAG exits column six and enters column seven at the polymerization temperature. Columns seven, eight, nine and ten are the reactor columns and are maintained at the polymerization temperature. TAG remains in the reactor columns for a residence time depending on the flow rate and exits into the storage tanks that are also under the same vacuum. The viscosity attained will depend on the residence time (flow rate) and the polymerization temperature. The results are shown in Tables 5 and 6. TABLE 5 Viscosities of Triacylglycerol Oligomers for Various Residence Times and Temperatures. RESIDENCE TEMPER- VIS- TRIACYLGLYCEROL TIME ATURE COSITY SOYBEAN  24 hours 285 C. 32 p COTTONSEED  8 hrs 318 C. 154 p  50% 13.5 hrs   295 C. 22 p SUNFLOWERSEED + 50% SOYBEAN CORN 13 hrs 295 C. 43 p 50% SOYBEAN + 13 hrs 303 C. 11 p 50% CANOLA TUNG

TABLE 6 Viscosity and Molecular Weight of Triacylglycerols Oligomers TRIACYLGLYCEROL VISCOSITY, CP MOL. WEIGHT MWD SOYBEAN 12400 132785 57.5 SOYBEAN 3207 5569 3.7

Skin color of face strongly depends on the type and amount of melanin and hemoglobin existing in the skin and varies widely according to several factors such as race, physiological conditions, age, sex, and seasonal variation. Face skin color is not uniform. It differs depending on whether it is the color of the forehead, forecheek, or sidecheek. Skin color was measured using photoelectric colorimeters and with the aid of computers, cosmetics were formulated using TAGOS to exactly match skin colors. The formulation given below was used to prepare cosmetic colors. Component % Standard No. 1 Cosmetic Brown-Lt 5.00 TAGOS Emulsion 95.00 Standard No. 2 Raw Sienna 5.00 TAGOS Emulsion 95.00 Standard No. 3 85% cosmetic Green + 5.00 15% Cosmetic Red TAGOS Emulsion 95.00

An emulsion consisting of water and TAGOS was prepared using a lecithin sludge as the emulsifying agent. Lecithin sludge is the concentrated mixture of lecithin and water resulting from the degummer. TAGO, 62.7 gms, and lecithin sludge (50-60%), 21.2 gms, are mixed and heated to 70° C. Water, 176.8 gms, is heated in a separate container to 70° C. and then added to the TAGO and lecithin sludge mixture. The solution is stirred and allowed to cool. The pigment is added and the mixture is homogenized.

A Lovibond Tintometer was used to measure skin color. The instrument was standardized according to a procedure using a gray scale and magnesium oxide standard. Measurements were made on the right cheek, left cheek, and the forehead. The skin color of 234 females was measured using the Lovibond Tintometer. This data is given in Table 9.

A thin layer of cosmetic preparation was placed on a filter paper and allowed to dry. The probe from the Lovibond Tintometer is placed directly on the dry cosmetic color preparation and the color determined and recorded. This data is given in Table 8.

A computer program was written for a Radio Shack Tridos 80 Computer to perform the calculations. Color matching functions of Banks (1977) were used to write the computer program. The program is written in four parts and is given in Table 7. The program produces tristimulus values, ratio of the standard cosmetic preparation to match the skin color, and the difference between the skin color and the calculated color match formulation. These results are given in Table 9. TABLE 7 Computer Program for Color Matching - Four Parts Part 1 ‘ FORMULA’ 1 DIM TR(39), TY(39), TB(39), E(39), EY(39), EZ(39) 10 REM CALCULTAION OF CHROMATICITY COORDINATRES AND TRISTIMULUS VALUES CALL TRISTIM 20 REM READ LOVIBOND SPECTRAL INTERNAL TRANSMITTANCES 40 FOR I = 0 TO 39 50 READ TR(I), TY(I), TB(I) 60 NEXT 70 REM READ CIE 1931 COLOR-MATCHING FUNCTIONS WEIGHTED BY RELATIVE SPECTRAL POWER DISTRIBUTIONS OF CIE STANDARDS 80 FOR I = 0 TO 39 90 READ EX(I), EY(I), EZ(I) 100 NEXT 130 DATA .90258, .02889, .99815 131 DATA .90352, .12593, .99809 132 DATA .90439, .25435, .99788 133 DATA .90603, .39957, .99711 134 DATA .90737, .52037, .99573 135 DATA .90824, .61634, .99363 136 DATA .90886, .70289, .99111 137 DATA .90858, .77822, .98800 138 DATA .90722, .84481, .98338 139 DATA .90444, .89471, .97459 140 DATA .89819, .92976, .96004 141 DATA .88633, .95277, .94109 142 DATA .86526, .96755, .92316 143 DATA .83257, .97738, .89900 144 DATA .79598, .98364, .87326 145 DATA .77392, .98754, .84574 146 DATA .78952, .99040, .83553 147 DATA .83317, .99195, .85049 148 DATA .87817, .99236, .86792 149 DATA .91300, .99247, .85702 150 DATA .93628, .99179, .81808 151 DATA .95268, .99073, .77002 152 DATA .96362, .98933, .76498 153 DATA .97109, .98768, .77420 154 DATA .97648, .98599, .77827 155 DATA .98053, .98438, .77386 156 DATA .98348, .98333, .76119 157 DATA .98572, .98287, .76656 158 DATA .98753, .98279, .78191 159 DATA .98892, .98330, .83172 160 DATA .99012, .98405, .88572 161 DATA .99117, .98449, .93507 162 DATA .99194, .98510, .96744 163 DATA .99247, .98627, .98466 164 DATA .99303, .98789, .99228 165 DATA .99336, .98912, .99587 166 DATA .99365, .99014, .99719 167 DATA .99402, .99108, .99770 168 DATA .99420, .99160, .99790 169 DATA .99430, .99210, .99800 180 DATA .004, .000, .020 181 DATA .019, .000, .089 182 DATA .085, .002, .404 183 DATA .329, .009, 1.57 184 DATA 1.238, .037, 5.949 185 DATA 2.997, .122, 14.628 186 DATA 3.975, .262, 19.938 187 DATA 3.915, .443, 20.638 188 DATA 3.362, .694, 19.299 189 DATA 2.272, 1.058, 14.972 190 DATA 1.112, 1.618, 9.461 191 DATA .363, 2.358, 5.274 192 DATA .052, .3.401, 2.864 193 DATA .089, 4.833, 1.520 194 DATA .576, 6.462, .712 195 DATA 1.523, 7.934, .388 197 DATA 4.282, 9.832, .086 198 DATA 5.880, 9.841, .039 199 DATA 7.322, 9.147, .020 200 DATA 8.417, 7.992, .016 201 DATA 8.984, 6.627, .010 202 DATA 8.949, 5.316, .007 203 DATA 8.325, 4.176, .002 204 DATA 7.070, 3.153, .002 205 DATA 5.309, 2.190, .000 206 DATA 3.693, 1.443, .000 207 DATA 2.349, .886, .000 208 DATA 1.361, .504, .000 209 DATA .708, .259, .000 210 DATA .369, .134, .000 211 DATA .171, .062, .000 212 DATA .082, .029, .000 213 DATA .039, .014, .000 214 DATA .019, .006, .000 215 DATA .008, .003, .000 216 DATA .004, .002, .000 217 DATA .002, .001, .000 218 DATA .001, .001, .000 219 DATA .001, .000, .000 300 REM CALCULATIONS OF TRISTIMULUS VALUES 310 U = 0 320 V = 0 330 W = 0 340 PRINT “INPUT Y” INPUT Y 350 PRINT “INPUT R” INPUT R 360 PRINT “INPUT B” INPUT B 370 FOR I = 0 TO 39 380 RYB = ((TR(I))[R)*((TY(I)[Y))*((TB(I)[B)) 390 U = U + ( RYB * EX(I)) 400 V = V + ( RYB + EY(I)) 410 W = W + ( RYB + EZ(I)) 420 NEXT 430 UVW = U + V + W 440 UBAR = U/UVW 450 VBAR = V/UVW 460 WBAR = W/UVW 470 X =U: LPRINT “X = ”;X 480 Y1 = V: LPRINT “Y = ”;Y1 490 Z = W: LPRINT “Z = ”;Z 500 OPEN “O”,1, “VALUES” 510 PRINT#1,X;Y1;Z 520 CLOSE 1 530 OPEN“O”,1,“LOVIBOND” 540 PRINT#1,Y;R;B 550 CLOSE 1 560 RUN “FORMULA1” Part 2 ‘FORMULA1’ 10 DIM TR(15), TY(15), TB(15), ME(16,3), T(16,3), Y(3), R(3), B(3), F(1), D(16,16) 40 FOR I = 0 TO 15 50 READ TR(I), TY(I), TB(I) 60 NEXT 132 DATA .90439, .25435, .99788 134 DATA .90737, .52037, .99573 136 DATA .90886, .70289, .99111 138 DATA .90722, .84481, .98338 140 DATA .89819, .92976, .96004 142 DATA .86526, .96755, .92316 144 DATA .79598, .98364, .87326 146 DATA .78952, .99040, .83553 148 DATA .87817, .99236, .86792 150 DATA .93628, .99179, .81808 152 DATA .96362, .98933, .76498 154 DATA .97648, .98599, .77827 156 DATA .98348, .98333, .76119 158 DATA .98753, .98279, .78191 160 DATA .99012, .98405, .88572 162 DATA .99194, .98510, .96744 330 FOR I = 1 TO 3 350 READ Y(I), R(I), B(I) 355 LPRINT “ ”:LPRINT Y(I), R(I), B(I) 360 NEXT 365 LPRINT “ ”:LPRINT “T1”, “T2”, “T3” 367 OPEN“O”,1,“DYES” 370 J = 0 380 FOR I = 0 TO 15 385 J = J + 1 390 FOR N = 1 TO 3 410 Q = (TR(I)[R(N))*(TY(I)[Y(N))*(TB(I)[(N)) 420 T(J,N) = (1−Q)[2/(2*Q) 430 NEXT 440 PRINT#1, T(J,1); T(J,2); T(J,3) 445 LPRINT “ ” : LPRINT T(J,1), T(J,2) T(J,3) 450 NEXT 460 CLOSE 1 465 GOTO 600 470 J = 0 480 OPEN “O”,1,“SAMPLE” 505 LPRINT “ ”: LPRINT “F”, “D” 510 FOR I = 0 TO 15 520 J = J + 1 530 Q = (TR(I)[X2)*(TY(I)[X1)*(TB(I)[X3) 540 F(J) = (1−Q)[2/(2*Q) 550 D(J,J) = −((4*Q)*(1−Q)+((1−Q)[2)*2)/(4*(Q[2)) 560 PRINT#1, F(J);D(J,J) 565 LPRINT “ ”:LPRINT F(J), D(J,J) 570 NEXT 580 CLOSE 1 590 RUN “FORMULA2” 600 OPEN“I”,1,“LOVIBOND” 610 INPUT#1,X1,X2,X3 620 CLOSE 1 630 GOTO 470 700 DATA 1.9, 3.7, 0 710 DATA 3.6, 4.0, 0 720 DATA 1.4, 1.2, 0 Part 3 “FORMULA2” 100 DIM ME(16,3), D(16,16), B(3,16), M(3,16), F(16,1), R(3,3), A(3,3), V(3,1),T(16,3), C(3,1) 105 LPRINT “ ”: LPRINT “EX-BAR, “EY-BAR”, “EZ-BAR” 110 OPEN“I”,1, “FUNCTION” 120 FOR I = 1 TO 16 140 INPUT#1, M(1,I), M(2,I), M(3,I) 170 NEXT 180 CLOSE 1 190 OPEN “1”,1,“SAMPLE” 200 FOR I = 1 TO 16 210 INPUT#1, F(I,1), D(I,1) 215 D(I,1), = 1/D(I,1) 220 NEXT 230 CLOSE 1 240 FOR 1 = 1 TO 3 250 FOR J = 1 TO 16 260 B(I,J) = 0 270 FOR K = 1 TO 16 280 B(I,J) = B(I,J) + M(I,K)*D(K,J) 290 NEXT K 300 NEXT J 310 NEXT I 315 FORJ = 1 TO 16 316 LPRINT “ ”:LPRINT B(1,J),B(2,J),B(3,J) 317 NEXT 320 OPEN “I”,1,“DYES” 330 FOR I = 1 TO 16 340 INPUT#1, T(I,1), T(I,2), T(I,3) 350 NEXT 360 CLOSE 1 370 FOR I = 1 TO 3 380 FOR J = 1 TO 3 390 R(I,J) = 0 400 FOR K = 1 TO 16 410 R(I,J) = R(I,J) + B(I,K)*T(K,J) 420 NEXT K 430 NEXT J 440 NEXT I 445 GOSUB 1000 450 GOSUB 18000 460 FOR I = 1 TO 3 470 C(I,1) = 0 480 FOR K = 1 TO 16 490 C(I,1) = C(I,1) + B(I,K)*F(K,1) 500 NEXT K 510 NEXT I 520 FOR I = 1 TO 3 530 V(I,1) = 0 540 FOR K = 1 TO 3 550 V(I,1) = V(I,1) + A(I,K)*C(K,1) 560 NEXT K 570 NEXT I 580 LPRINT “ C1 EQUALS ” ; V(1,1): LPRINT “ ” 590 LPRINT “ C2 EQUALS ” ; V(2,1): LPRINT “ ” 600 LPRINT “ C3 EQUALS ” ; V(3,1): LPRINT “ ” 610 OPEN “O”,1, “INVERSE” 620 FOR I = 1 TO 3 630 PRINT#1, A(I,1);A(I,2);A(I,3) 640 NEXT 650 CLOSE 1 660 OPEN “O”,1, “CONCN” 670 PRINT#1, V(1,1); V(2,1); V(3,1) 680 CLOSE 1 690 RUN “FORMULA3” 1000 PRINT “THE MATRIX TO BE INVERTED IS: ”: PRINT 1010 FOR I = 1 TO 3: FOR J = 1 TO 3 : LPRINT R(I,J): NEXT J: PRINT : NEXT I 1020 RETURN 18000 CLS: REM SUBROUTINE TO INVERT AN N X N MATRIX. A(N,N) IS THE INPUT 18001 GOTO 18009: INPUT “DO YOU WANT DOUBLE PRECISION”;A$ 18002 IF LEFT$(A$,1) = “N” THEN 18009 18004 DEFDBL A-H, O-Z 18009 DEFINT I,J,N 18010 N = 3 18050 FOR I = 1 TO N: A(I,1) = 1: NEXT 18052 CLS: PRINT “ YOUR MATRIX IS: ”:PRINT 18054 FOR I = 1 TO N: FOR J = 1 TO N: I3!=R(I,J):PRINT I3!; :NEXT:PRINT :NEXT 18060 I1 = I1 + 1: IF I1 = N + 1 THEN 18210: REM WE'RE THROUGH! 18070 IF R(I1,I1) = 0 THEN GOSUB 18130 : REM INTERCHANGE ROWS 18080 REM NORMALIZE DIAGONAL ELEMENT AND ZERO COLUMN IN OTHER ROWS. 18090 Q = R(I1,I1): FOR J = I1 TO N: R(I1,J) = R(I1,J)/Q: NEXT 18095 FOR J = 1 TO N: A(I1,J) = A(I1,J)/Q: NEXT 18100 FOR I = 1 TO N: IF I = I1 THEN 18117 18105 Q = R(I,I1) 18110 FOR J = I1 TO N: R(I,J) = R(I,J) − Q*R(I1,J): NEXT 18115 FOR J = 1 TO N: A(I,J)=A(I,J)−Q*A(I1,J): NEXT 18117 NEXT I 18120 GOTO 18060 18130 REM INTERCHANGE ROWS TO PREVENT ZERO DIVIDE 18140 I2 = I1: IF I2 = N THEN 18170 18150 I2 = I2 = I2 + 1: IF I2 = N THEN 18170 18160 IF R(I2,I1) = 0 AND I2<N THEN 18150 18170 IF I2 = N THEN PRINT “ DETERMINENT = 0 ! ! ! ”: STOP 18180 FOR I = I1 TO N 18190 T = R(I1,I):R(I1,I) = R(I2,I): R(I2,I) = T 18200 S = A(I1,I):A(I1,I) = A(I2,I):A(I2,I) = S:NEXT: RETURN 18210 GOSUB 18230; FOR I = 1 TO N: FOR J = 1 TO N: PRINT A(I,J): NEXT J: PRINT: 18220 RETURN 18230 PRINT “ THE INVERSE OF YOUR MATRIX IS : ”: PRINT:RETURN 19000 REM INPUT ELEMENTS BY ROW 19010 PRINT “ENTER THE ELEMENTS ONE AT A TIME BY ROW AND PRESS ENTER” 19020 FOR I = 1 TO N: FOR J = 1 TO N 19030 INPUT R(I,J): NEXT J,I 19040 GOTO 18050 Part 4 ‘FORMULA3’ 100 DIM FM(16,1), TM(3,1), T(16,3), V(3,1) M(3,16), RM(16,1) 110 OPEN “I”,1, “DYES” 120 FO;R I = 1 TO 16 130 INPUT#1, T(I,1), T(I,2), T(I,3) 140 NEXT 150 CLOSE 1 160 OPEN “I”,1, “CONCN” 170 INPUT#1, V(1,1), V(2,1), V(3,1) 180 CLOSE 1 190 FOR I = 1 TO 16 200 FM(I,1) = 0 210 J = 1 TO 3 220 FM(I,1) = FM(I,1) + T(I,J) + V(J,I) 230 NEXT J 240 NEXT I 250 GOTO 500 260 OPEN “I”,1, “FUNCTION” 270 FOR I = 1 TO 16 280 INPUT#1, M(1,I), M(2,I), M(3,I) 290 NEXT 300 CLOSE 1 310 FOR I = 1 TO 3 320 TM(I,1) = 0 330 FOR K = 1 TO 16 340 TM(I,1) = TM(I,1) + M(I,K)*RM(K,I) 350 NEXT K 360 NEXT I 370 OPEN “ O”,1, “TRISTIM” 380 PRINT#1, TM(1,1);TM(2,1);TM(3,1) 390 CLOSE 1 400 LPRINT “ ” : LPRINT “ ” 410 LPRINT “TRISTIMULUS VALUES FOR MATCH”: LPRINT “ ” 420 LPRINT “ X = ”; TM(1,1):LPRINT “ ” 430 LPRINT “ Y = ”; TM(2,1):LPRINT “ ” 440 LPRINT “ Y=“ ”; TM(3,1):LPRINT “ ” 450 RUN “FORMULA4” 500 FOR I = 1 TO 16 510 B1 = 2*(1+FM(I,1)) 520 B2 = B1[2 530 RM(I,1) = (B1 − SQR(B2−4))/2 540 NEXT 550 GOTO 260 Part 5 “FORMULA4” 6000 REM CALCULATIONS OF COLOR DIFFERENCE 6005 DIM DT(3,1), TM(3,1), A(3,3), DC(3,1), V(3,1), VXS(1), VYS(1), VZS(1) 6010 PRINT “INPUT VX, VY, VZ FOR SAMPLE” 6020 INPUT VXS(1), VYS(1), VZS(1) 6060 PRINT “INPUT VX, VY, VZ FOR MATCH” 6065 INPUT MXV: INPUT MYV: INPUT MZV 6067 FOR I = 1 TO 1 6210 DVY = ((0.23)*(VYS(I) − MYV))[2 6215 D1VXY = (( VXS(I) − VYS(I)) − (MXV −MYV))[2 6220 D2VZYY = (VZS(I) −VYS(I)) − (MZV − MYV) 6225 D3VZY = ((0.4)*(D2VZYY))[2 6230 DE = (DVY + D1VXY + D3VZY)[(½) 6235 DE = 40*DE 6237 NEXT 6238 LPRINT “ ”; LPRINT “ ” 62440 LPRINT “ THE VALUE FOR THE COLOR DIFFERENCE IS ”; DE; LPRINT “ ” 6250 PRINT “ TO CONTINUE ITERATION , ‘ENTER’ 1. ”: PRINT “ ” 6260 PRINT “ TO DISCONTINUE ITERATION, ‘ENTER’ 2. ”: PRINT “ ” 6270 INPUT ZZ 6280 ON ZZ GOTO 10000, 6300 6300 END 10000 OPEN “I”, 1,1 “VALUES” 10010 INPUT#1, X, Y, Z 10020 CLOSE 1 10030 OPEN “I”,1, “TRISTIM” 10040 INPUT#1, TM(1,1), TM(2,1), TM(3,1) 10050 CLOSE 1 10060 DT(1,1) = X − TM(1,1) 10070 DT(2,1) = Y − TM(2,1) 10080 DT(3,1) = Z − TM(3,1) 10090 OPEN “I” ,1, “INVERSE 10100 FOR I = 1 TO 3 10110 INPUT#1, A(I1,). A(I2,), A(I3) 10120 NEXT 10130 CLOSE 1 10140 FOR I = 1 TO 3 10150 DC(I,1) = 0 10160 FOR K = 1 TO 3 10170 DC(I,1) = DC(I,1) + A(I,K)*DT(K,I) 10180 NEXT K 10190 NEXT I 10200 OPEN “I”,1, “CONCN” 10210 INPUT#1, V(1,1), V(2,1), V(3,1) 10220 CLOSE 1 10230 V(1,1) = V(1,1) + DC(1,1) 10240 V(2,1) = V(2,1) + DC(2,1) 10250 V(3,1) = V(3,1) + DC(3,1) 10260 LPRINT “ ”; LPRINT “ ” 10270 LPRINT “ C1 = ”;V(1,1) LPRINT “ ” 10280 LPRINT “ C2 = ”;V(2,1) LPRINT “ ” 10290 LPRINT “ C3 = ”;V(3,l) LPRINT “ ” 10300 OPEN “O”,1, “CONCN” 10310 PRINT#1, V(1,1), V(2,1), V(3,1) 10320 CLOSE 1 10330 RUN “FORMULA3” 10340 END

TABLE 8 Color of Standard Soybean Cosmetic Formulations - NUMBER Y R B 1 1.9 3.7 0 2 3.6 4 0 3 1.3 1.2 0

TABLE 9 Skin Color of Females- NUM COLOR RANGE HUE VALUE CHR X-BAR Y-BAR Z-BAR Y DE 12 1 1 7.53 YR 4.86 4.03 0.4034 0.3733 0.2234 19 1-4 29 2 2 6.79 YR 4.43 3.54 0.4 0.3619 0.2388 15 4-7 13 3 2 6.63 YR 6 3.5 0.3761 0.3563 0.2677 30 11-12 12 4 4 5.29 YR 3.59 2.99 0.3964 0.356 0.2546 10 7-9 15 5 4 5 YR 5.34 3.75 0.3848 0.3562 0.259 23  9-10 22 6 5 4.27 YR 4.68 3.01 0.3777 0.3509 0.2717 17 12-13 5 7 6 3.06 YR 5.73 4.62 0.3968 0.3528 0.2504 27 10-11 10 8 6 3.26 YR 4 2.19 0.3668 0.3403 0.2929 12 17-18 44 9 7 2.5 YR 4 2.86 0.3832 0.344 0.2727 12 14-15 36 10 7 2.47 YR 4.68 3.36 0.3818 0.3464 0.2718 17 13-14 19 11 8 10 R 4.68 3.71 0.388 0.3417 0.2708 17 15-16 17 12 8 10 R 6 5.38 0.3633 0.3478 0.2889 30 16-17

Preparation of Triacylglycerol Oligomers Cosmetics 1. Cold Cream Soybean Z- 6 40.1% Lecithin Sludge  8.1% Water 51.8% 2. Lotion Soybean Z - 3 30.1% Lecithin Sludge  8.1% Water 60.8% 3. Foundation Soybean Z - 8 25.0% Lecithin Sludge  8.0% Water 57.0% Pigment 10.0% 4. Lipstick Soybean Z - 10 40.0% Lecithin  8.0% Water 42.0% Pigment 10.0% 5. Pucker Paint Soybean Z - 5 37.3% Lecithin Sludge  8.0% Water 44.7% Pigment 10.0% 6. Blusher Soybean Z - 6 37.9% Lecithin Sludge  8.0% Water 44.1% Pigment 10.0% 7. Mascara Soybean Z - 9 48.0% Lecithin Sludge  8.0% Water 34.0% Carbon Black 10.0%

Color has three qualities which are hue, value and chroma or intensity. Hue is the quality which distinguishes one color from another, for example red or blue. It is the name of the color family. The lightness or darkness of a color is called value. We can visualize how light or how dark a color is by comparing it with a value scale showing black at the bottom and white at the top. The third dimension of color is chroma or intensity. It is often thought of as the strength or weakness of a color. We can think of intensity as the degree to which a color departs from a neutral gray of the same value.

A pleasing combination of colors is known as a color harmony. One of the greatest teachers of color harmony is nature. This phenomenon is apparent in everything that grows. Nature presents a protusion of colors, beautifully arranged and spaced so as to present a pleasing spectacle to the eye. Flowers of strong and weak colors are striking against their background. Trees in the fall of the year are never more harmonious than in their bright color schemes of red, orange, yellow, and purple against the background of clear blue sky with fading green grass and brown earth in the foreground. These colors brings a change of hues, values, and chroma, and presents a beautiful color scheme. There are four general ways to combine colors; contrast in hue, value, chroma and area. The Munsell color theory suggests three paths for color harmony. The first path is vertical with rapid changing value. We refer to this color harmony as SOPHISTICATED. The second path is lateral. This is a rapid change of hues adjacent on the color wheel. We refer to this color harmony as EXOTIC. The third path is inward. The inward path leads to the neutral center and onto the opposite on the Munsell color wheel. We refer to this color harmony as PROVACATIVE.

Using the color of the skin, the color of the eyes, the color of the hair and a related red, a computer program was developed to produce sophisticated, exotic, and provocative color harmony schemes for skin colors as shown in Table 10. The harmony schemes are set forth in Tables 11-14. TABLE 11 Color Harmony Data for Color No. 35 COLOR HUE VALUE CHROMA HAIR 4.5 R 2.3 4.5 EYES 6.7 B 3.4 1.2 SKIN 3.5 yr 4.4 3.3 RELATED RED 4.4 r 2.3 1.4

TABLE 12 Color Harmony Data for Color No. 45 COLOR HUE VALUE CHROMA HAIR 4.5 4.5 4.5 EYES 6.7 6.7 6.7 SKIN 8.9 8.9 8.9 RELATED RED 6.7 6.7 6.7

TABLE 13 Cosmetic Wardrobe Listing for Color No. 35 COSMETIC CODE COLOR DIFFERENCE 1.98 FOUNDATION DEEP COCOA #11 BLUSHER TITIAN LIPSTICK #11 DAZZLE DUST VIOLET PUCKER PAINT CURRANT

TABLE 14 Cosmetic Wardrobe for Color No. 45 COSMETIC CODE COLOR DIFFERENCE 0.456 FOUNDATION DEEP COCOA #11 BLUSHER BURGUNDY LIQUID LINER BROWN MASCARA BLACK LIPSTICK 4 LIPGLOSS 4 DAZZLE DUST BRONZE FROST PUCKER PAINT AMETHYST

Heat-set web offset ink was introduced in the 1950's as a printing process and is used for the production of magazines, catalogues and brochures. All heat-set inks are expected to fulfill exacting criteria, in addition to properties of cold-set ink, such as high gloss and dry quickly in an oven. Heat-set inks are dried by passing the printed web of paper through an oven using high velocity hot air; sufficient to raise the temperature 100-140° C. TAGOS ink has been formulated which meet the criteria of heat-set web offset ink and does not need to be passed through an oven for drying (Tables 15-24). This is accomplished by formulating printing ink using TAGOS of viscosity above 300 poises to obtain high gloss and rub-off resistance. Quick drying is accomplished by using a drying agent. TABLE 15 Soybean Oligomer Printing Ink - Formula I SUBSTANCE PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 71 CLAYTONE HY 9

TABLE 16 Soybean Oligomer Printing Ink - Formula II SUBSTANCE PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 70 CLAYTONE HY 9 COBALT ACETATE 1

TABLE 17 Soybean Oligomer Printing Ink - Formula III SUBSTANCE PERCENT CARBON BLACK 15 SOYBEAN OLIGOMER Z - 10 30 SOYBEAN OLIGOMER Z - 3 40 CLAYTONE HY 9 COBALT ACETATE 1

TABLE 18 Soybean Oligomer Printing Ink - Formula IV SUBSTANCE PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 61 CLAYTONE HY 9 POLYOL 10

TABLE 19 Cottonseed Oligomer Printing Ink - Formula V SUBSTANCE PERCENT CARBON BLACK 20 COTTONSEED OLIGOMER 71 CLAYTONE HY 9 COBALT ACETATE 1

TABLE 20 Sunflowerseed Oligomer Printing Ink - VI SUBSTANCE PERCENT CARBON BLACK 20 SUNFLOWERSEED OLIGOMER 71 CLAYTONE HY 9 COBALT ACETATE 1

TABLE 21 Corn Oligomer Printing Ink - VII SUBSTANCE PERCENT CARBON BLACK 20 CORN OLIGOMER 71 CLAYTONE HY 9 COBALT ACETATE 1

TABLE 22 N,N′-di-n-butyl-N_(a)-lauroyl Glutamide(BLG) Soybean Oligomer Printing Ink - VIII SUBSTANCE PERCENT CARBON BLACK 20 BLG-SOYBEAN OLIGOMER 71 CLAYTONE - HY 9

TABLE 23 Thermosetting Epoxy Printing Ink SUBSTANCE PERCENT EPOXY(I) SOYBEAN* 70 PHTHALO BLUE PIGMENT 15 SOLVENT 5 CLAYTONE HY 5

TABLE 24 Fountain Solution SUBSTANCE PERCENT A B DICK UNIVERSAL 95 T-BUTYL HYDROPEROXIDE 5

In screen printing the ink is forced through the open areas of a stencil supported on a mesh of synthetic fabric stretched across a frame. The ink is mechanically forced through the mesh onto the substrate underneath by drawing a squeegee across the stencil. These inks are high H viscous, low tack, short cure times, and good color retention after several wash cycles. TAGOS were formulated to meet these criteria (Tables 25-31). TABLE 25 Screen Printing Ink - Formula I SUBSTANCE PERCENTAGE CI PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER 30 SOYBEAN OLIGOMER Z - 6 50

TABLE 26 Screen Printing Ink - Formula II SUBSTANCE PERCENTAGE CI PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER 30 SOYBEAN OLIGOMER X - Y 50

TABLE 27 Screen Printing Ink - Formula III SUBSTANCE PERCENT CI PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER Z-6 30 SOYBEAN OLIGOMER Z-6 25 SOYBEAN OLIGOMER X - Y 25

TABLE 28 Screen Printing Ink - Formula IV SUBSTANCE PERCENT BLUE DYE 10 SOYBEAN OLIGOMER Z - 6 25 WATER 74.98 THICKNER 0.1 COBALT ACETATE 0.1

TABLE 29 Screen Printing Ink - Formula V SUBSTANCE PERCENT BLUE DYE 10 COTTONSEED OLIGOMER 25 WATER 74.98 THICKNER 0.1 COBALT ACETATE 0.1

TABLE 30 Screen Printing Ink - Formula VI SUBSTANCE PERCENT BLUE DYE 10 SUNFLOWERSEED OLIGOMER 25 WATER 74.98 THICKNER 0.1 COBALT ACETATE 0.1

TABLE 31 Screen Printing Ink - Formula VII SUBSTANCE PERCENT BLUE DYE 10 CORN OLIGOMER 25 WATER 74.98 THICKNER 0.1 CORN 0.1

The inks were printed on cotton and coated cotton fabrics and allowed to dry. The printed fabrics were then washed and dried. The color was measured before and after each wash cycle to determine color fastness (Tables 32-33). TABLE 32 Color Fastness of Screen Printed Uncoated Cotton Fabrics Gray INK Change- FORMULA L* a* b* L* a* b* Difference I 36.31 43.35 12.60 37.59 38.00 9.97 3.00 6.10 IV 38.99 −14.21 −39.57 40.96 −12.85 −35.00 3.00 5.16

TABLE 33 Color Fastness of Screen Printed Coated Cotton Fabrics INK COLOR BEFORE COLOR AFTER Gray Change- FORMULA L* a* b* L* a* b* Difference I 37.63 47.09 12.42 39.55 44.52 9.44 3.00 4.37 IV 38.99 −14.21 −39.57 40.96 −12.85 −35.00 3.00 5.16

Although many valuable products are fabricated each day from fibers, these items could never exist unless a finish had been applied to the fibers during the extrusion or spinning process. Fabric finishing is intended to provide a special performance characteristics or properties to a textile fabric. This can be the development of dimensional control or resistance to wrinkling during use. The characteristics may be the provision of permanent crease and smooth drying performance or the requirement for the fabric to withstand subsequent processing steps. There may be the need for a finish to impart resistance to end use exposure, i.e., water or oil repellency or resistance to crocking or bleeding. Of equal importance is the need to provide the finished fabric with improved or changed aesthetic properties. TAGOS were developed for applications in sizing and finishing.

Solutions to size fabrics were made according to the formula given in Table 34. TAGOS were soybean, cottonseed, sunflowerseed, and corn. Strips of gauzy cotton fabric (5×30 cm were padded twice at 25 C to ca. 110% wet pick-up, followed by drying at 120 C for 3 minutes and conditioning for 48 hours at 65% relative humidity and at room temperature.

Textile finishers were made using soybean, cottonseed, sunflower seed, and corn oligomers according to the formula given in Table 35. Poplin cotton fabric pieces (30×45 cm) were padded twice at room temperature in the finish solution to ca. 80% wet pick-up, followed by drying (100C/3 min.) and curing (160 C/3 min.). The cured samples were then given an after wash in a bath containing 1 g/l sodium carbonate along with 1 g/l on triton X-100 at 55 C for 15 minutes/rinsed, and air dried, and conditioned. TABLE 34 Formula for Textile Sizers SUBSTANCE PERCENTAGE TAGO 12 TRITON X - 100 5 WATER 83

TABLE 35 Formula for Textile Finishers SUBSTANCE PERCENTAGE TAGO 25 WATER 65 MAGNESIUM CHLORIDE 5 HEXAHYDRATE TRITON X-100 5

Historically, reactions on polymers have been of major importance, as they have made possible the applications of cellulose as textile fibers, plastics, coatings, and even explosives. Reactions of polymers can occur with oxygen, irradiation, heat, moisture, and bacterial attack which induces the problem of “aging” of polymeric materials. The most important of them are atmospheric oxygen and irradiation, since they are most likely to induce chain scission. Polymers can undergo chemical reactions by chemical modification of the functional groups of the polymers. As discussed earlier, a Diels-Alder diene synthesis was historically used as a basis for explaining the polymerization of TAGOS which is most often referred to in the literature. Most investigators agree with the formation and presence of hydroxyl groups, carboxylic acid groups, cyclic compounds, and double bonds during thermal polymerization. These functional groups along with the ester group provide the basis for producing polymers from TAGOS.

An equivalency based on hydroxyl number of the glycol and assumed hydroxyl number of TAGOS per molecule was calculated. The hydroxyl number for glycol was two and the hydroxyl number for TAGO varied for each experiment. The equivalency mass for glycol was the molecular weight divided by two. The equivalency mass for TAGOS was obtained by dividing the apparent molecular weight by the hydroxyl number for each experiment. Apparent molecular weights were determined by gel permeation chromatography. An illustrative example was the formation of complexes between soybean oligomer (SBO) and ethylene and propylene glycol (Table 36). The apparent molecular weight of SBO was 10,000.

A series of experiments were conducted using N,N′-di-butyl-N_(a)-lauroyl glutamide (BLG) to crosslink TAGOS. One gram of BLG was dissolved in 99 grams of TAGOS and heated to 150° C. The solution viscosity increased depending on the amount of BLG added. TABLE 36 Triacylglycerol Oligomer Complexes with Ethylene and Propylene Glycol TAGOS VISCOSITY HYDROXYL* MOL. WT. GLYCOL RATIO VISCOSITY SOYBEAN 22683 cp 10 10000 ETHYLENE 1::1 17733 cp SOYBEAN 22683 cp 10 140000 PROPYLENE 1:01 17983 cp

When ethylene glycol, 10 grams, was mixed with SBO, 300 grams, the solution thickened and became very turbid. The mixture was heated up to temperatures of about 120° C. and a white vapor was given off. The mixture was removed from the hot plate for thirty minutes after which time the mixture was replaced on the hot plate and heating continued. No vapors were given off after heating for 3.75 hours. After heating for more than six hours the mixture became completely clear with the appearance of small crystal like substances at the bottom if the flask. After more than nine hours of heating, the mixture was removed from the heat and allowed to cool. As it cooled down to room temperature, it became a turbid viscous mixture.

SBO, 306 grams, was mixed with propylene glycol, 10 grams, in an Erlenmeyer flask. The mixture remained clear after mixing. The mixture was heated to a temperature of about 120° C. The mixture was heated to a temperature of about 115° C. at which time white vapors were given off. However, the mixture remained clear. After more than eight hours of heating, the mixture was removed from the hot plate and cooled to room temperature. At room temperature, the mixture became very turbid and viscous.

Soybean oligomer Z-6(TAGO), 500 grams, is heated to 145° C. and 1000 g of myrcene and 10 grams of di-tert-bu peroxide is added. The reaction is continued for 6 hours at 140-150° C. The modified TAGO is treated with 0.05% Co and heated in a dryer.

Maplewood shavings, 16.1 grams, and soybean oligomer Z-6,53.5 grams, were mixed together until all shavings of maplewood were covered with the oligomer. The mixture was placed in a 8½ cm diameter×7 mm thick brass dish. Hot air was blown over the mixture for one hour. The mixture was placed in a convection oven at 75° C. for 26 hours. The board was removed and allowed to cool to room temperature and examined. The board was spongy.

Lawn grass with long stems and long blade-like leaves was cut into small pieces and dried. The grass sample was then placed into a mill and reduced to small fragments. A small mesh screen was used to separate the smallest pieces from the larger pieces. The smaller pieces were used for the preparation. Grass, 2.0 grams, was mixed with SBO, 200 grams, in an Erlenmeyer flask. The mixture was stirred and placed on a hot plate. After approximately one hour of heating the mixture turned a very dark green. The mixture was heated for a total of twenty one hours, removed from the hot plate and allowed to cool to room temperature. The viscosity of the mixture was determined (Table 37). TABLE 37 Viscosity Data for Complex Between Triacylglycerol Oligomers and Gramineae (Grass) TAGOS TAGO VISCOSITY COMPLEX VISCOSITY SOYBEAN 22,683 cp 33,367 cp

Johnson's pure cotton balls, made from 100% pure, non-chlorine bleached cotton, were purchased from a local drug store. One cotton, which weighed 0.3 grams, was pulled into small pieces and added one at a time to an Erlenmeyer flask containing 203 grams of SB(Z-6) which had been heated to 100° C. The mixture was stirred and placed on a hot plate. After heating for approximately seven hours at 110° C., the cotton started to form a gelatinous mass. It was not observable whether the liquid portion of the mixture was also becoming more gelatinous. Continued heating of the mixture resulted in the cotton becoming almost completely gelatinous. The mixture was removed from the hot plate after 40 hours of heating. The viscosity of the liquid portion was measured (Table 38). TABLE 38 Data for Complex Between Triacylglycerol Oligomers and Cotton TRIACYLGLYCEROL OLIGOMER COMPLEX VISCOSITY, P SOYBEAN (Z-6) >8,000,000 cp

Removal of ink from paper substrate is done commercially using ink removal solutions containing hazardous materials. It has been previously shown that TAGOS can be emulsified using water and a surfactant. Paper printed with TAGOS inks are easily dissolved in a solvent system using non-hazardous water-based cleaning solutions which emulsifies the ink and can be reused several times before it has to be replaced. The ink solution is filtered to remove the deinked paper slurry which can then be further processed to produce recycled paper. TABLE 39 Formulation of Ink Removal Solution #1 CONSTITUENT PERCENT PART A 89.07 WATER 85.07 SWS 0.1122 DYE 1.68 MONOETHANOLAMINE 2.25 NA4EDTA 2.81 DIPROPYLENEGL; 3.37 YCOLMETHYLETHER WITCONATE 90 K 4.27 PART B* 10.93 TRITON X-100 64.04 HYAMINE 8.51 SCENT 27.45

TABLE 40 Formulation of Ink Removal Solution #2 CONSTITUENT PERCENT TRITON X-100 1 POTASSIUM HYDROXIDE (37.4%) 13.37 WATER 85.63

Approximately three drops of red ink was placed on a 5″×8″ piece of white paper and drawn down with a putty knife making an ink strip approximately 3″ in width. A length of approximately 2″ was cut and used for the test.

In one Erlenmeyer flask was placed 100 ml of formula #1 (Table 39) cleaning solution along with the test specimen. In another Erlenmeyer flask was placed 100 ml of formula #2 (Table 40) cleaning solution along with the test specimen. Both solution were shaken and allowed to stand. Periodically on several occasions they were shaken again. Ink began to be removed immediately with formulation #1 as evidence by the solution forming a reddish color. With formulation #2, color was being removed as evidence by the fading of the test specimen.

The mixture obtained from printed paper is filtered and the solution decanted. The paper slurry remaining is mixed with and emulsion prepared using soybean oligomer Z-6(25%), triton X-100(5%), and water (70%). The mixture is filtered and then dried by passing through pads heated to 75° C. A sheet of recycled paper is formed.

TAGOS interaction with metals and water were examined. The examination was to determine differences in the interaction between metal-TAGO complex and water-TAGO complex. Soybean oligomer Z-6 and X-Y, 5 grams each, were placed in separate containers of 95 grams of distilled water. The mixtures were stirred and allowed to stand at room temperature. The same procedure was repeated with 0.2 m potassium hydroxide solution.

Both soybean oligomers X-Y and Z-6 had formed two layers. The aqeuous layer was slightly turbid and a white oily layer. Upon standing at room temperature for a long period of time, soybean oligomer Z-6 formed a rubbery, spongy mass. This mass is probably due to the interaction of air, water and the oligomer.

Water was added to a beaker which contained soybean oligomer crosslinked with BLG. The mixture was heated to boiling. The sides of the beaker were scraped with a spatula. Upon cooling, polymer particles were floating in the water. The particles were removed from the water and allowed to dry. Upon drying, the small particles formed clear plastic pieces. The plastic pieces were very elastic and stretched when pulled. The plastic pieces were soft and spongy.

Upon addition of 0.2 m KOH to soybean oligmer X-Y, the solution turned milky white with no formation of oil droplets. A foamy layer was on top. Upon addition of 0.2 m KOH to soybean oligmer, X-6, it also formed a milky/cloudy solution with a foamy layer on top. However, upon standing for a long period of time, soybean oligomer X-Y produces large amount of foam when shaken with no visible large particles present. The solution, however, is still turbid. In the case of soybean oligomer Z-6, the mixture does not produce a lot of foam when shaken, and it contained solid particles.

A monoterpene, myrcene, H₂C═CHC(═CH₂)—CH₂CH₂CH═C(CH₃)₂, was added to soybean oligomer Z-6. A terpene has hydrocarbon chains of alternating double and single bonded carbon atoms. The terpene may be monocyclic, dicyclic or acyclic compounds. Examples of terpenes include, but are not limited to: myrcene, dipentene, limonene, citral, pinene, carvone, citronellal, ocimene, linalool, phellandrene, carvacrol, and thymol. The terms dipentene or limonene include d-limonene, l-limonene and mixtures of the two.

The reaction between myrcene and the soybean oligomer was exothermic and instantaneous with a large increase in temperature once the reaction began. The product from the reaction was a gel indicating a complex was formed. Myrcene cross links due to oxidation forming composites that will cure faster than soybean oligomer due to the bonds added. This allows for the development of an ink with the properties of heat-set inks without using high temperature ovens to cure the ink.

Degummed soybean oil was thermally polymerized at 285° C. using tert-butyl peroxide as a catalyst. The reaction was allowed to proceed for 4.5 hours. The viscosity at 25° C. was 241 centiposes. At a temperature of 285° C. the viscosity was 150 centiposes after 4.5 hours. This indicates an increase in the rate of reaction, not the time of the reaction. Thus, a catalyst allows thermal polymerization of soybean oil at a faster rate.

A finishing solution containing solvent and an emulsion of soybean oligomer Z-6 was prepared. A piece of untreated cotton fabric was passed through the solution and placed in an oven to dry. The fabric was placed in an infrared (IR) spectroscopy machine. FIGS. 5-8 show the spectra of various combinations. A computerized analysis of the infrared spectrum of untreated cotton fabrics finished with soybean oligomer Z-6 show the formation of a terminal alkyne ether with the structural formula HC≡C—O—R. The terminal alkyne ether is shown in a band at 670 cm⁻¹ and a confirming band between 2085 cm⁻¹ and 2135 cm⁻¹. An ester linkage is first formed between the carboxylic acid group of the soybean oligomer and the alcohol group of the cellulose. This ester linkage then decomposes to form the terminal alkyne ether during high temperature curing.

The following is the mechanism:

Maintaining the ester linkage and not allowing the degradation leading to formation of the terminal alkyne ether linkage may improve the finishing properties of the soybean oligomer. This may establish a linkage between native cotton and cellulosic plants for developing products such as fibers and paper.

TAGOS may be used to improve the physical properties and optical properties of recycled pulp and absorbent products that could benefit from tensile strength under wet conditions. Virgin pulp is replaced with the oligomers and TAGOS is added to the absorbent product. In one preferred embodiment, the virgin pulp is replaced with the oligomers, thermally polymerized with soybean oil to form a SBOMP. The soybean oligomers act as a pulp strengthening agent. The first step in the process is to prepare an initial emulsion by heating (a) 25 grams of soybean oligomer (SBO)[S-Y, Z-6, Z-10] and 5 grams of triton surfactant X-100, and (b) 70 grams of water in separate containers to 70° C. The emulsion is prepared by adding the water to the SBO and triton X-100 mixture. The emulsion consists of 25% SBO. SBOMP is prepared by stirring together for one hour at a pH of 8.0 at room temperature mixtures containing 80%-20%, 60%-40%, 40%-60%, and 20%-80% SBO emulsion to recycle pulp. The mixture is then filtered to remove the bulk quantity of liquid and the remaining material is passed through rollers to further remove water. The material is then air dried at room temperature. Variation of SBO emulsion concentration, pH, mixing temperature and time will be varied, if necessary, until the desired results are obtained.

A sample of the material is then characterized by infra-red spectophotometric analysis (Rensch, et al, 1993). The characterization includes the esterification of the —OH groups associated with the cellulosic material indicated by the characteristic absorption bands of the resulting cellulosic esters and the degree of hydroxyl conversion determined by the ratio of peak intensity of hydroxyl and carbonyl stretching vibrations. Examination of the spectra at 670 cm⁻¹ and between 2085 cm⁻¹ and 2135 cm⁻¹ for the presence of formation of terminal alkyne ether.

The following tests are performed on SBOMP to ascertain the physical properties. The TAPPI method relating to each test is given in parenthesis:

-   -   1. Handsheet Preparation (T 205 sp—02—“Forming Handsheets for         Physical Tests of Pulp”);     -   2. Basis Weight (T 220 s-01—“Physical Testing of Pulp         Handsheets”);     -   3. Caliper (T 220 sp-01—“Physical Testing of Pulp Handsheets”);     -   4. Bulk (T 220 sp-01—“Physical Testing of Pulp Handsheets”);     -   5. Density (T 220 sp-01—“Physical Testing of Pulp Handsheets”);     -   6. Tear (T 414 om-98—“Initial Tearing Resistance of Paper”);     -   7. Burst (T 403 om-97—“Bursting Strength of Paper”);     -   8. Tensile (T 494 om-01—“Tensile Properties of Paper and         Paperboard (Using Constant Rate of Elongation Appratus)”);     -   9. Fiber Analysis (identifies and quantifies pulp types present         in the pulp mixture);     -   10. MorFi Fiber Length Analysis (includes fiber length, width,         kink, curl, and coarseness);     -   11. Gluability (T 698 cm-03—“Determination of Wetting Tension of         Polyethylene and Polypropylene Films and Coatings”;     -   12. Size (T 458 cm-94—“Surface Wettability of Paper”; and     -   13. Printability (T 698 cm-03—“Determination of Wetting Tension         of Polyethylene and Polypropylene Films and Coatings”.

The following optical tests are performed on SBOMP to ascertain the optical properties. The TAPPI method relating to each test is given in parenthesis:

-   -   1. Brightness (T 525 om-02—“Diffuse Brightness of Pulp”);     -   2. Color (T 527 om-02—“Color of Paper and Paperboard”); and     -   3. Opacity (T 519 om-02—“Diffuse Opacity of Paper”).

Each sample of SBOMP is evaluated based on the degree of ester conversion, physical properties, and optical properties. A similar set of characteristic data is obtained for recycle pulp, virgin pulp, and a mixture of virgin pulp and recycle pulp. The strengthening or lack thereof is calculated from a comparison of physical and optical properties. A similar process may be conducted when adding TAGOS to an absorbent product (e.g., disposable diapers, feminine hygiene products, adult incontinence products, household wipes, and the like).

All materials referenced herein, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference in their entirety as though set forth herein in particular.

Thus, in accordance with the present invention, there has been provided triacylglycerol oligomers and methods for making and using same that fully satisfies the objectives and advantages set forth above. Although the invention has been described in conjunction with the specific drawings and language set forth above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the invention. 

1. A method for using a triacylglycerol oil oligomer to improve recycled paper pulp properties, comprising the steps of: refining crude triacylglycerol oil to produce a refined triacylglycerol oil; polymerizing the refined triacylglycerol oil to produce a triacylglycerol oil oligomer; mixing the triacylglycerol oil oligomer with a surfactant to form an emulsion; and mixing the emulsion with recycled pulp.
 2. The method of claim 1, wherein the crude triacylglycerol is a crude soybean oil.
 3. The method of claim 1, wherein in the step of refining the crude triacylglycerol oil to produce a refined triacylglycerol oil, the refining step is a degumming process wherein gums and waxes are removed from the crude triacylglycerol oil.
 4. The method of claim 1, wherein the polymerizing step occurs under a vacuum.
 5. The method of claim 1, wherein in the polymerizing step, a complexing agent is added to the refined triacylglycerol oil.
 6. The method of claim 5, wherein the complexing agent is a Group II or Group VIII metal compound.
 7. The method of claim 6, wherein the complexing agent is Ca(OH)₂.
 8. The method of claim 1, wherein the polymerizing step is conducted at a temperature of from 200° C. to about 360° C.
 9. The method of claim 1, wherein the polymerizing step is conducted at a temperature of 340° C., Ca(OH)₂ is added to the refined triacylglycerol oil, and the polymerizing step is conducted under a vacuum.
 10. A method for using a triacylglycerol oil oligomer to improve absorbent product properties, comprising the steps of: refining crude triacylglycerol oil to produce a refined triacylglycerol oil; polymerizing the refined triacylglycerol oil to produce a triacylglycerol oil oligomer; mixing the triacylglycerol oil oligomer with a surfactant to form an emulsion; and adding the emulsion to an absorbent product.
 11. The method of claim 10, wherein the crude triacylglycerol is a crude soybean oil.
 12. The method of claim 10, wherein in the step of refining the crude triacylglycerol oil to produce a refined triacylglycerol oil, the refining step is a degumming process wherein gums and waxes are removed from the crude triacylglycerol oil.
 13. The method of claim 10, wherein the polymerizing step occurs under a vacuum.
 14. The method of claim 10, wherein in the polymerizing step, a complexing agent is added to the refined triacylglycerol oil.
 15. The method of claim 14, wherein the complexing agent is a Group II or Group VIII metal compound.
 16. The method of claim 15, wherein the complexing agent is Ca(OH)₂.
 17. The method of claim 10, wherein the polymerizing step is conducted at a temperature of from 200° C. to about 360° C.
 18. The method of claim 10, wherein the polymerizing step is conducted at a temperature of 340° C., Ca(OH)₂ is added to the refined triacylglycerol oil, and the polymerizing step is conducted under a vacuum. 